Biodegradable PLGA oligomers were synthesized to feature a hybrid organic-inorganic moiety, POSS, incorporated at the center of each chain by using it as the ring-opening initiator. After end-capping with vinyl groups, the macromers were photocured into networks with POSS content ranging from 10 to 41 wt %. Increasing POSS inclusion increased the crystallinity of the network while decreasing the degradation rate due to its hydrophobic and nonhydrolyzable properties. It was found that co-curing PLGA oligomers with and without POSS in the backbone could be utilized to create networks with a reduced POSS loading level, at a given cross-link density, allowing tuned crystallinity. Hydrolytic degradation of the co-cured networks was slower than for the PLGA homonetwork but still led to complete degradation after 14 weeks in PBS buffer at 37°C. The networks exhibited versatile shape memory properties, exploiting the combination of covalent cross-linking and the glass transition, POSS-phase melting temperature, or both as the shape-switching trigger. Using the glass transition was found to yield the best shape fixing, while the best recovery percentages (∼100%) were achieved when the melting transition was used. One network, with 24 wt % POSS, was able to be fixed in a temporary shape by POSS crystallization and to largely preserve this shape during degradation. After 4 weeks and 60% mass loss, 50% of the initial deformation still remained while the PLGA network (shape fixed through T g ) had recovered fully. Our findings are expected to impact future design of biodegradable polymers with shape memory, having revealed the precise tuning of properties possible through controlled placement of a crystallizable and hydrophobic moiety in the polymer network chain.